EP3013879B1 - Pièces moulées de pur résistants à l'hydrolyse. - Google Patents

Pièces moulées de pur résistants à l'hydrolyse. Download PDF

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EP3013879B1
EP3013879B1 EP14730462.0A EP14730462A EP3013879B1 EP 3013879 B1 EP3013879 B1 EP 3013879B1 EP 14730462 A EP14730462 A EP 14730462A EP 3013879 B1 EP3013879 B1 EP 3013879B1
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bisphenol
polyurethane
weight
acid
polyesterols
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EP3013879A1 (fr
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Amir Doroodian
Yan He
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/487—Polyethers containing cyclic groups
    • C08G18/4879—Polyethers containing cyclic groups containing aromatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/14—Manufacture of cellular products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1808—Catalysts containing secondary or tertiary amines or salts thereof having alkylene polyamine groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3237—Polyamines aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271—Hydroxyamines
    • C08G18/329—Hydroxyamines containing aromatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
    • C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
    • C08G18/425—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids the polyols containing one or two ether groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00—Manufacture of cellular products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0033—Foam properties having integral skins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/0066—≥ 150kg/m3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2410/00—Soles

Definitions

  • the present invention relates to a process for the preparation of polyurethane moldings having a density of 150 to 850 g / L in which (a) organic polyisocyanates with (b) compounds having at least two isocyanate-reactive hydrogen atoms containing polyesterol (b1) and at least one compound (b2) obtainable by alkoxylation of bisphenol A as starter with propylene oxide (c) propellant, (d) catalyst, and (e) optionally other excipients and / or additives mixed into a reaction mixture, in a mold and allowed to react to a polyurethane molding , Further, the present invention relates to polyurethane moldings, obtainable by such a method and the use of these moldings as a steering wheel, seat, armrest and in particular as a shoe sole.
  • foamed polyurethanes are known and can be used for a wide variety of applications. In most applications, these are produced on the basis of polyethers or polyesters as polyols.
  • the polyester polyurethanes have better mechanical properties than the polyether polyurethanes.
  • the PESOL polyurethanes (polyesterol based polyurethanes) show improved swelling resistance to organics such as e.g. iso-octane. This swelling resistance is an important requirement for use as a safety shoe and can not be met by Polyetherpolyurethan.
  • Disadvantage of polyester polyurethanes is that they are prone to hydrolysis in a warm and humid environment. Above all, foams are affected because of their large surface in comparison to the volume.
  • polyesterols are used for the production of polyurethanes based on polyesterols, which are obtained by polycondensation of C4 to C6 dicarboxylic acids with polyfunctional alcohols.
  • these polyurethanes have the disadvantage that they have only insufficient hydrolytic stability.
  • these C4 to C6 dicarboxylic acids are replaced by more hydrophobic dicarboxylic acids. So describes US 2005124711 microcellular polyester polyurethanes obtained from polyesterols derived from dimeric fatty acids.
  • WO 2004/050735 describes the use of polyesterols based on a combination of ortho-phthalic acid and a dicarboxylic acid having 8-12 carbon atoms to improve the stability to hydrolysis.
  • WO 03/070801 A1 discloses polyurethane foams having a density of 250 to 700 g / L (claim 8), which are used for the production of shoe soles (page 1, lines 5-6) and which have a very good hydrolysis resistance (page 9, lines 14-21 ).
  • a disadvantage of these polyesters with improved hydrolytic stability is that used raw materials are expensive.
  • the mechanical properties compared to polyurethanes on the basis of classic polyesterols which are obtained by polycondensation of C4 to C6 dicarboxylic acids with polyhydric alcohols, worse.
  • the iso-octane swelling whereby these solutions are only partially suitable for the production of safety shoes.
  • the object of the present invention was to provide elastomeric polyurethane moldings, in particular elastomeric polyurethane integral foams based on polyesterols, which have improved hydrolytic stability and excellent mechanical properties, which are particularly suitable as sole material for safety shoes.
  • the object according to the invention can be achieved by an elastomeric polyurethane molding having a density of 150 to 850 g / l, which can be prepared by a process which comprises (a) organic polyisocyanates having (b) compounds having at least two isocyanate-reactive hydrogen atoms containing polyesterol ( b1) and at least one compound (b2) obtainable by alkoxylation of bisphenol A as starter with propylene oxide (c) blowing agent, (d) catalyst, and (e) optionally other excipients and / or additives mixed into a reaction mixture, in a mold and ausreagieren to a polyurethane molding.
  • the polyurethane molded articles according to the invention are elastomeric polyurethane foams, preferably polyurethane integral foams.
  • an elastomeric polyurethane foam is to be understood as meaning polyurethane foams according to DIN 7726 which after a short deformation of 50% of the thickness according to DIN 53 577 have no permanent deformation over 5% of their initial thickness after 10 minutes.
  • Polyurethane integral foams in the context of the invention are polyurethane foams according to DIN 7726 with a marginal zone, which due to the shaping process has a higher density than the core understood.
  • the total raw density averaged over the core and the edge zone is between 150 g / L and 850 g / L, preferably from 180 g / L to 750 g / L, particularly preferably 200 g / L to 650 g / L.
  • the organic and / or modified polyisocyanates (a) used for producing the polyurethane foam moldings according to the invention comprise the known from the prior art aliphatic, cycloaliphatic and aromatic di- or polyfunctional isocyanates (component a-1) and any mixtures thereof.
  • MMDI monomeric metanediphenyl diisocyanate
  • 4'-metanediphenyl diisocyanate 4,4'-metanediphenyl diisocyanate
  • 2,4'-metanediphenyl diisocyanate the mixtures of monomeric metanediphenyl diisocyanates and higher nuclear homologs of meta diphenyl diisocyanate
  • polymer MDI tetramethylene diisocyanate
  • HDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • TDI 2,4- or 2,6-toluene diisocyanate
  • 4,4'-MDI is used.
  • the preferred 4,4'-MDI may contain from 0 to 20 weight percent 2,4'-MDI and minor amounts, to about 10 weight percent, of allophanate or uretonimine modified polyisocyanates. It is also possible to use small amounts of polyphenylene polymethylene polyisocyanate (polymeric MDI). The total amount of these high-functionality polyisocyanates should not exceed 5% by weight of the isocyanate used.
  • the polyisocyanate component (a) is preferably used in the form of polyisocyanate prepolymers.
  • These polyisocyanate prepolymers are obtainable by reacting polyisocyanates (a-1) described above, for example at temperatures of 30 to 100 ° C., preferably at about 80 ° C., with compounds having at least two isocyanate-reactive hydrogen atoms (a-2) to form the prepolymer become.
  • Such compounds having at least two isocyanate-reactive hydrogen atoms are known to the person skilled in the art and are described, for example, in US Pat. Kunststoffhandbuch, volume 7, Polyurethane ", Carl Hanser Verlag, 3rd edition 1993, chapter 3.1 , Preferably, the polyesterols described under b) are used.
  • the polyols (b) contain polyesterols (b1) and at least one compound (b2), obtainable by alkoxylation of an aromatic starter molecule.
  • the polyesterols used are polyesterols having at least two hydrogen atoms reactive toward isocyanate groups. Polyesterols preferably have a number average molecular weight of greater than 450 g / mol, particularly preferably greater than 500 to less than 8,000 g / mol and in particular from 600 to 3,500 g / mol and a functionality of from 2 to 4, in particular from 2 to 3.
  • Polyester polyols (b1) can be prepared, for example, from organic dicarboxylic acids having 2 to 12 carbon atoms, preferably aliphatic dicarboxylic acids having 4 to 6 carbon atoms and polyhydric alcohols, preferably diols having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms.
  • Suitable dicarboxylic acids are, for example: succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid and terephthalic acid.
  • the dicarboxylic acids can be used both individually and in admixture with each other.
  • dicarboxylic acid derivatives for example dicarboxylic acid esters of alcohols having 1 to 4 carbon atoms or dicarboxylic acid anhydrides.
  • dicarboxylic acid mixtures of succinic, glutaric and adipic acid in proportions of, for example, 20 to 35: 35 to 50: 20 to 32 parts by weight, and in particular adipic acid.
  • dihydric and polyhydric alcohols are: ethanediol, diethylene glycol, 1,2- or 1,3-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10 -Decandiol, glycerol and trimethylolpropane.
  • ethanediol diethylene glycol, 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol.
  • polyesterpolyols from lactones, for example ⁇ -caprolactone or hydroxycarboxylic acids, for example ⁇ -hydroxycaproic acid.
  • the organic e.g. aromatic and preferably aliphatic polycarboxylic acids and / or derivatives and polyhydric alcohols catalyst-free or preferably in the presence of esterification catalysts, conveniently in an atmosphere of inert gas, such. Nitrogen, carbon monoxide, helium, argon and the like. in the melt at temperatures of 150 to 250 ° C, preferably 180 to 220 ° C, optionally under reduced pressure, to the desired acid number, which is preferably less than 10, more preferably less than 2, polycondensed.
  • inert gas such. Nitrogen, carbon monoxide, helium, argon and the like.
  • the esterification mixture at the abovementioned temperatures up to an acid number of 80 to 30, preferably 40 to 30, under normal pressure and then under a pressure of less than 500 mbar, preferably 50 to 150 mbar, polycondensed.
  • Suitable esterification catalysts are, for example, iron, cadmium, cobalt, lead, zinc, antimony, magnesium, titanium and tin catalysts in the form of metals, metal oxides or metal salts.
  • the polycondensation may also be carried out in the liquid phase in the presence of diluents and / or entraining agents, e.g.
  • the organic polycarboxylic acids and / or derivatives and polyhydric alcohols are advantageously polycondensed in a molar ratio of 1: 1 to 1.8, preferably 1: 1.05 to 1.2.
  • polyesterols (b1) are polymer-modified polyesterols, preferably graft polyesterols.
  • This is a so-called polymer polyesterol which usually has a content of, preferably thermoplastic, polymers of from 5 to 60% by weight, preferably from 10 to 55% by weight, particularly preferably from 15 to 50% by weight and in particular from 20 to 40 wt .-%, has.
  • polymer polyesterols are, for example, in WO 05/098763 and EP-A-250351 and are usually prepared by free-radical polymerization of suitable olefinic monomers, for example styrene, acrylonitrile, (meth) acrylates, (meth) acrylic acid and / or acrylamide, in a graft-based polyesterol.
  • suitable olefinic monomers for example styrene, acrylonitrile, (meth) acrylates, (meth) acrylic acid and / or acrylamide
  • the side chains are generally formed by transferring the radicals from growing polymer chains to polyesterols or polyetherols.
  • the polymer-polyesterol contains predominantly the homopolymers of the olefins dispersed in unchanged polyesterol.
  • the monomers used are acrylonitrile, styrene, preferably acrylonitrile and styrene.
  • the monomers are polymerized in the presence of further monomers, a macromer, ie an unsaturated, free-radically polymerizable polyol, a moderator and using a free-radical initiator, usually azo or peroxide compounds, in a polyesterol or polyetherol as the continuous phase.
  • a macromer ie an unsaturated, free-radically polymerizable polyol
  • a moderator and using a free-radical initiator, usually azo or peroxide compounds, in a polyesterol or polyetherol as the continuous phase.
  • a free-radical initiator usually azo or peroxide compounds
  • the macromers are incorporated into the copolymer chain.
  • This forms block copolymers with a polyester and a polyacrylonitrile-styrene block, which act as phase mediators in the interface of continuous phase and dispersed phase and suppress the agglomeration of the polymer polyesterol particles.
  • the proportion of macromers is usually 1 to 20 wt .-%, based on the total weight of the monomers used to prepare the polymer polyol.
  • polymer polyesterol is present, this is preferably present together with further polyesterols. Particularly preferably, the proportion of polymer polyol is greater than 5 wt .-%, based on the total weight of component (b).
  • the polymer polyesterols may be contained, for example, in an amount of from 7 to 90% by weight, or from 11 to 80% by weight, based on the total weight of the component (b).
  • compound (b2) obtainable by alkoxylation of an aromatic starter molecule is used.
  • aromatic starter molecules include for example phenylenediamine, 2,3-, 2,4- and 2,6-toluenediamine (TDA), 4,4'-, 2,4'- and 2,2'-diaminodiphenylmethane (MDA), polymeric MDA, and bisphenols.
  • the aromatic starter molecule has at least two benzene rings, and is more preferably a bisphenol or a derivative of a bisphenol.
  • derivatives are compounds in which hydrogen atoms on aromatic or on aliphatic C atoms are replaced by halogen atoms or hydrocarbon radicals, such as alkyl or aryl radicals. These hydrocarbon radicals can be unsubstituted or substituted, for example by halogen atoms, oxygen, sulfur or phosphorus. These can be used individually or in the form of mixtures.
  • Bisphenols include bisphenol A, bisphenol AF, bisphenol AP, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol FL, bisphenol G, bisphenol M, bisphenol P, bisphenol PH, bisphenol S, bisphenol TMC and bisphenol Z. Particularly preferred Bisphenol A and / or bisphenol S and in particular bisphenol A used as an aromatic starter molecule.
  • the compounds (b2) are prepared by alkoxylation of bisphenol A as a starter with propylene oxide.
  • they can be prepared by anionic polymerization of bisphenol A with propylene oxide using alkali metal hydroxides, such as.
  • alkali metal hydroxides such as.
  • sodium or potassium hydroxide or alkali metal such as.
  • sodium, sodium or potassium or potassium are obtained as catalysts.
  • Compounds (b2) according to the invention obtainable by alkoxylation of bisphenol A as starter with propylene oxide, preferably have a hydroxyl number of 80 to 400 mg KOH / g, particularly preferably 100 to 320 mg KOH / g and in particular 120 to 250 mg KOH / g.
  • Alkoxylation products of bisphenol A starter with propylene oxide are sold under the trade name SynFac® by Milliken Chemical.
  • the proportion of component (b2), based on the total weight of component (b), is preferably from 0.01 to 10% by weight, more preferably from 0.1 to 6% by weight and in particular from 0.5 to 4% by weight .-%.
  • polyesterols (b1) and compound (b2) obtainable by alkoxylation of bisphenol A as a starter with propylene oxide
  • polyols which are customary in polyurethane chemistry and have a number-average molecular weight of greater than 500 g / mol, for example polyetherols.
  • the proportion of the further polyols is preferably less than 40 wt .-%, more preferably less than 20 wt .-%, most preferably less than 10 wt .-%, more preferably less than 5 wt .-% and in particular 0 wt .-%, based on the total weight of polyesterols (b) and the other polyols.
  • the compounds having at least 2 isocyanate-reactive hydrogen atoms may contain so-called chain extenders and / or crosslinking agents.
  • Chain extenders and / or crosslinking agents are understood as meaning substances having a molecular weight of preferably less than 450 g / mol, more preferably from 60 to 400 g / mol, chain extenders having 2 isocyanate-reactive hydrogen atoms and crosslinking agent 3 isocyanate-reactive hydrogen atoms. These can preferably be used individually or in the form of mixtures. Preference is given to using diols and / or triols having molecular weights of less than 400, more preferably from 60 to 300 and in particular from 60 to 150.
  • chain extenders (f) particular preference is given to using monoethylene glycol, 1,4-butanedio
  • chain extenders, crosslinking agents or mixtures thereof are expediently used in amounts of from 1 to 60% by weight, preferably from 1.5 to 50% by weight and in particular from 2 to 40% by weight, based on the weight of the component b).
  • blowing agents c) are present in the production of polyurethane foam moldings.
  • These propellants c) may contain water.
  • blowing agent c) in addition to water additionally generally known chemically and / or physically acting compounds can be used.
  • Chemical blowing agents are compounds which form gaseous products by reaction with isocyanate, such as, for example, water or formic acid.
  • Physical blowing agents are understood as compounds which are dissolved or emulsified in the starting materials of polyurethane production and evaporate under the conditions of polyurethane formation.
  • blowing agent employed is a mixture containing at least one of these blowing agents and water, in particular water as the sole blowing agent. If no water is used as blowing agent, preferably only physical blowing agents are used.
  • the content of water in a preferred embodiment of 0.1 to 2 wt .-%, preferably 0.2 to 1.5 wt .-%, particularly preferably 0.3 to 1.2 wt .-%, based on the total weight of components (a) to (e).
  • reaction of the components (a) to (e) is added as an additional blowing agent hollow microspheres containing physical blowing agent.
  • the hollow microspheres can also be used in admixture with the abovementioned propellants.
  • the hollow microspheres usually consist of a shell of thermoplastic polymer and are filled in the core with a liquid, low-boiling substance based on alkanes.
  • the production of such hollow microspheres is for example in US Pat. No. 3,615,972 described.
  • the hollow microspheres generally have a diameter of 5 to 50 microns. Examples of suitable hollow microspheres are available from Akzo Nobel under the trade name Expancell® ®.
  • the hollow microspheres are generally added in an amount of 0.5 to 5 wt .-%, based on the total weight of components b), c) and f).
  • catalysts (d) for the preparation of the polyurethane foams preference is given to using compounds which greatly accelerate the reaction of the compounds with at least two isocyanate-reactive hydrogen atoms (b) with the organic, optionally modified polyisocyanates (a).
  • amidines such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine
  • tertiary amines such as triethylamine, tributylamine, dimethylbenzylamine, N-methyl-, N-ethyl-, N-cyclohexylmorpholine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylbutanediamine, N, N, N ', N'-tetramethylhexanediamine, pentamethyldiethylenetriamine, tetramethyldiminoethyl ether, bis (dimethylaminopropyl) urea, Dimethylpiperazine, 1,2-dimethylimidazole, 1-azabicyclo- (3,3,0) -octane and preferably 1,4-diazabicyclo- (2,2,2) -octane and alkanolamine
  • organic metal compounds preferably organic tin compounds such as stannous salts of organic carboxylic acids, e.g. Stannous (II) acetate, stannous octoate, stannous (II) ethyl hexoate and stannous laurate and the dialkyltin (IV) salts of organic carboxylic acids, e.g.
  • organic tin compounds such as stannous salts of organic carboxylic acids, e.g. Stannous (II) acetate, stannous octoate, stannous (II) ethyl hexoate and stannous laurate and the dialkyltin (IV) salts of organic carboxylic acids, e.g.
  • the organic metal compounds can be used alone or preferably in combination with strongly basic amines. Preferably, only amine catalysts are used as catalysts (d).
  • Preferably used are 0.001 to 5 wt .-%, in particular 0.05 to 2 wt .-% catalyst or catalyst combination, based on the weight of component (b).
  • auxiliaries and / or additives (e) may also be added to the reaction mixture for the preparation of the polyurethane foams. Mention may be made, for example, release agents, fillers, dyes, pigments, hydrolysis protectants, odor-absorbing substances and fungistatic and / or bacteriostatic substances.
  • Suitable release agents are: reaction products of fatty acid esters with polyisocyanates, salts of polysiloxanes containing amino groups and fatty acids, salts of saturated or unsaturated (cyclo) aliphatic carboxylic acids having at least 8 carbon atoms and tertiary amines, and in particular internal release agents such as carboxylic esters and / or amides prepared by esterification or amidation of a mixture of montanic acid and at least one aliphatic carboxylic acid having at least 10 carbon atoms with at least difunctional alkanolamines, polyols and / or polyamines having molecular weights of 60 to 400 g / mol, such as in EP 153 639 discloses mixtures of organic amines, metal salts of stearic acid and organic mono- and / or dicarboxylic acids or their anhydrides, such as in DE-A-3 607 447 or mixtures of an imino compound, the metal salt of a carboxylic acid and optional
  • Fillers are the conventional, customary organic and inorganic fillers, reinforcing agents, weighting agents, coating compositions, etc., to be understood.
  • inorganic fillers such as silicate minerals, for example phyllosilicates, such as antigorite, bentonite, serpentine, hornblende, amphiboles, chrysotile and talc, metal oxides, such as kaolin, aluminas, titanium oxides, zinc oxide and iron oxides, metal salts, such as chalk and barite, and inorganic pigments such as cadmium sulfide, zinc sulfide and glass, among others Preference is given to using kaolin (China Clay), aluminum silicate and coprecipitates of barium sulfate and aluminum silicate.
  • Suitable organic fillers are, for example: carbon black, melamine, rosin, cyclopentadienyl resins and graft polymers and also cellulose fibers, polyamide, polyacrylonitrile, polyurethane, polyester fibers based on aromatic and / or aliphatic dicarboxylic acid esters and in particular carbon fibers.
  • the inorganic and organic fillers can be used individually or as mixtures and are advantageously added to the reaction mixture in amounts of from 0.5 to 50% by weight, preferably from 1 to 40% by weight, based on the weight of components (a) to ( e), added.
  • polyester polyurethanes can be significantly improved by the addition of additives such as carbodiimides.
  • additives such as carbodiimides.
  • Such materials are commercially available under trade names such as e.g. Elastostab TM or Stabaxol TM available.
  • the starting components (a) to (e) are mixed together in amounts such that the equivalence ratio of NCO groups of the polyisocyanates (a) to the sum of the reactive hydrogen atoms of components (b) and (c) is 1: 0, 8 to 1: 1.25, preferably 1: 0.9 to 1: 1.15.
  • a ratio of 1: 1 corresponds to an isocyanate index of 100.
  • the isocyanate index is understood as meaning the stoichiometric ratio of isocyanate groups to isocyanate-reactive groups multiplied by 100.
  • the present invention furthermore relates to a polyurethane molded article obtainable by the process according to the invention.
  • the polyurethane foam moldings according to the invention are preferably prepared by the one-shot process with the aid of the low-pressure or high-pressure technique in closed, suitably tempered molds.
  • the molds are usually made of metal, eg aluminum or steel.
  • the starting components (a) to (e) are preferably mixed at a temperature of 15 to 90 ° C, more preferably from 25 to 55 ° C and optionally introduced the reaction mixture under elevated pressure in the mold.
  • the mixing can be carried out mechanically by means of a stirrer or a stirring screw or under high pressure in the so-called countercurrent injection method.
  • the mold temperature is expediently 20 to 160 ° C, preferably 30 to 120 ° C, particularly preferably 30 to 60 ° C.
  • the mixture of components (a) to (e) at reaction conversions of less than 90%, based on the isocyanate groups is referred to as the reaction mixture.
  • the amount of the reaction mixture introduced into the mold is such that the resulting moldings, in particular integral foam, have a density of preferably 150 g / L to 850 g / L, preferably from 180 g / L to 600 g / L, particularly preferably 200 g / L up to 500 g / l and in particular 220 to 400 g / l.
  • the degrees of densification for producing the integral polyurethane foams according to the invention are in the range from 1.1 to 8.5, preferably from 1.6 to 7.0.
  • the polyurethane moldings according to the invention are preferably used as a shoe sole and particularly preferably as an (intermediate) sole, for example for street shoes, sports shoes, sandals and boots.
  • the integral polyurethane foams according to the invention are used as a midsole for sports shoes or as sole material for high-heeled women's shoes.
  • polyurethane foams according to the invention can be used in the interior of transport vehicles, for example in cars, as steering wheels, headrests or control buttons or as chair armrests. Other uses are as an armrest for chairs or as motorcycle seats.
  • the starting materials were mixed and placed in a closed mold with the dimensions 20cm x 20 cm x 1 cm. All amounts in Table 1 to the starting materials are parts by weight.
  • the isocyanate index is 100 in all examples and comparative examples.
  • the test plates obtained were conditioned for 2 days under standard conditions before the mechanical characterization was carried out. The hardness, the rebound resilience according to DIN 53512, the tear strength according to DIN ISO 34-1, A, the tensile strength according to DIN 53504 and the elongation at break according to DIN 53543 were determined. To determine the hydrolysis properties, the test specimens were stored in accordance with DIN 53543 at 70 ° C.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)

Claims (7)

  1. Procédé de fabrication de corps moulés de polyuréthane ayant une densité de 150 à 850 g/l, selon lequel
    a) des polyisocyanates organiques sont mélangés avec
    b) des composés contenant au moins deux atomes d'hydrogène réactifs avec les isocyanates, contenant un polyestérol (b1) et au moins un composé (b2), pouvant être obtenu par alcoxylation de bisphénol A en tant que produit de départ avec de l'oxyde de propylène,
    c) un agent gonflant,
    d) un catalyseur et
    e) éventuellement d'autres adjuvants et/ou additifs,
    pour former un mélange réactionnel, qui est introduit dans un moule et laissé réagir pour former un corps moulé de polyuréthane.
  2. Procédé selon la revendication 1, caractérisé en ce que le composé (b2) présente un indice hydroxyle de 80 à 400 mg KOH/g.
  3. Procédé selon l'une quelconque des revendications 1 ou 2, caractérisé en ce que le polyestérol (b1) peut être obtenu par condensation d'acides dicarboxyliques de 4 à 10 atomes C avec un alcool aliphatique bifonctionnel et/ou trifonctionnel.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que le composant (b) contient moins de 10 % en poids d'autres polyols en plus des composants (b1) et (b2).
  5. Corps moulé de polyuréthane, pouvant être obtenu par un procédé selon l'une quelconque des revendications 1 à 4.
  6. Corps moulé de polyuréthane selon la revendication 5, caractérisé en ce que le corps moulé de polyuréthane est une semelle de chaussure.
  7. Utilisation d'un corps moulé de polyuréthane selon la revendication 5 en tant que semelle de chaussure.
EP14730462.0A 2013-06-28 2014-05-28 Pièces moulées de pur résistants à l'hydrolyse. Active EP3013879B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP14730462.0A EP3013879B1 (fr) 2013-06-28 2014-05-28 Pièces moulées de pur résistants à l'hydrolyse.
PL14730462T PL3013879T3 (pl) 2013-06-28 2014-05-28 Elementy kształtowe z poliuretanów odporne na hydrolizę

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP13174414.6A EP2818489A1 (fr) 2013-06-28 2013-06-28 Pièces moulées de PUR résistants à l'hydrolyse
EP14730462.0A EP3013879B1 (fr) 2013-06-28 2014-05-28 Pièces moulées de pur résistants à l'hydrolyse.
PCT/EP2014/061072 WO2014206679A1 (fr) 2013-06-28 2014-05-28 Corps moulés en polyuréthane résistants à l'hydrolyse

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EP3013879B1 true EP3013879B1 (fr) 2017-07-12

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EP14730462.0A Active EP3013879B1 (fr) 2013-06-28 2014-05-28 Pièces moulées de pur résistants à l'hydrolyse.

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EP (2) EP2818489A1 (fr)
KR (1) KR20160027080A (fr)
CN (1) CN105492483A (fr)
BR (1) BR112015032377A2 (fr)
ES (1) ES2643482T3 (fr)
PL (1) PL3013879T3 (fr)
PT (1) PT3013879T (fr)
WO (1) WO2014206679A1 (fr)

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EP2952531A1 (fr) * 2014-06-02 2015-12-09 Basf Se Pièce moulée élastique en base de polyurethane
RU2702351C2 (ru) * 2015-03-09 2019-10-08 Басф Се Полиуретановые формованные изделия с превосходной гибкостью при низких температурах
EP3333209B1 (fr) * 2016-12-07 2023-09-20 Henkel AG & Co. KGaA Matrice de résine de polyuréthane thermoplastique
CN109251304A (zh) * 2018-08-23 2019-01-22 合肥金菱电器有限公司 一种阻燃聚氨酯泡沫塑料及其制备方法
US20220251328A1 (en) * 2019-06-27 2022-08-11 Covestro Deutschland Ag Method for recovering raw materials from polyurethane products

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Publication number Publication date
ES2643482T3 (es) 2017-11-23
EP2818489A1 (fr) 2014-12-31
CN105492483A (zh) 2016-04-13
BR112015032377A2 (pt) 2017-07-25
KR20160027080A (ko) 2016-03-09
PT3013879T (pt) 2017-10-11
WO2014206679A1 (fr) 2014-12-31
PL3013879T3 (pl) 2017-12-29
EP3013879A1 (fr) 2016-05-04
US20160145372A1 (en) 2016-05-26

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